CS257315B1 - Binder based on hydraulically active substances, especially cement clinker - Google Patents

Abstract

The solution relates to a binder based on hydraulically active substances, in particular cement clinker, which contains 0.005 to 0.5% of alkylolamides of linear alkylarylsulfonic acids or alkylolamides of sulfated fatty acids, or their salts or mixtures of these alkylolamides with esteramines or esteramides of these acids, where the number of carbon atoms in the alkyl of the acid is 10 to 20. Alkylolamine derivatives in combination with a sulfonated polyelectrolyte and an alkaline compound delay the onset of solidification of mixtures and improve their workability, positively influence the hydration process, stabilize the onset of solidification of gypsum-free cements under disruptive conditions. They can be advantageously used in the construction industry.

Description

The invention relates to a binder based on hydraulically active substances, in particular cement clinker.

Gypsum-free cements (hereinafter referred to as BS cements) represent a new type of inorganic binder, which is based on the synergistic action of an inorganic electrolyte (especially alkali carbonate, bicarbonate or hydroxide) and an anionic plasticizer (e.g. sulfonated polyelectrolytes such as lignin sulfonate and its derivatives, sulfonated lignin, sulfonated polyphenolate, etc.). The properties of these cements were described, for example, in articles by F. Škvára, M.

Rybinová: The gypsum-free portland cement, Cement and Concrete Research 15, 1 013 až 1 021 (1985), F. Škvára: Microstructure of hardened pastes of gypsum-free portland cements. Proc. 8th International Congress on Chemistry of Cements, section 2.2., Rio de Janeiro (1986) and further in a.o. 198 053, 203 212, 225 066.

An important feature of BS cements is the possibility of processing at a low water coefficient while maintaining good rheological properties. Due to the low porosity of the hardened cement stone, BS cements are characterized not only by high short-term and long-term strengths, but also by high corrosion resistance, the ability to harden at low and negative temperatures, and also by resistance to high temperatures. These engineering properties of BS cements were discussed, for example, in the articles: F. Škvára, L. Pekárek, B. Velička: The gypsum-free portland cement hydration and its thermal properties, Proceedings of the 8th Inter. Conf. Thermal Analysis 566 to 570, 1985, Bratislava; Ovčatenko G. I., F- Tamás: Properties of Alkali-lignosulfonate mixed cements, Epitoanyag 36, 353 to 358 (1984); L. G. Špynova et al. Peculiarities of cement compositions for longer use at negative temperatures, Cement (USSR), 11 (1985).

The composition of BS cements is known from patent and journal literature. From US 3, 689, 294 (Brunauer) and from the publication by M. Yudenfreund et al.: Hardened portland cement pastes of low porosity, Cement and Concrete Research 2, 313 to 330 (1972) the composition of a freely flowing expanding cement slurry (or mortars and concretes) based on ground cement clinker with a specific surface area of 600 to 900 m/kg is known, which contains at least 0.002 parts of a grinding additive and at least 0.002 5 parts of alkaline lignin sulfonate or alkaline earth lignin sulfonate or sulfonated lignin and at least 0.002 5 parts of alkaline carbonate, with a water coefficient in the range of 0.20 to 0.28. As grinding additives specified in these publications were Kraft lignin (alkali lignin), oleic acid, diethyl carbonate, ethoxylated nonylphenols with various numbers of ethoxyl groups, sodium dodecylbenzenesulfonate, a mixture of alkali sulfonates and sulfocarboxylates, sulfosuccinate, alkylated sulfosuccinates or mixtures of sulfosuccinates together with amines and alkyl sulfonates or with alkylphenol polyglycol ether, triethanolamine, ethylene glycol, alkylphenol sulfonates (especially alkylated diphenol oxide disulfonates). The last-mentioned substance of the diphenyl oxide disulfonate type is stated as optimal for the preparation and processing of BS cements.

This composition of BS cements was specified in US 3,959,004 (Stryker), where the authors came to the conclusion that instead of alkali carbonate, alkali bicarbonate could be used in gypsum-free cements. Some problems associated with the use of BS cements (short onset of setting) were addressed in US 4,168,985 (Kolář et al.), which described a binder based on cement clinker containing cement with a specific surface area greater than 15 m/kg, which has 5 to 99.9% by weight of cement particles with a specific surface area of 250 to 3,000 m/kg and containing 5 to 95% by weight of cement particles with a size of up to 5 microns and at least 0.0025 parts by weight of a lignin sulfonate-based substance, further 0.05 to 80 parts by weight of water, 0.01 to 8% by weight of an alkaline compound, preferably a carbonate, and other additives modifying the onset of setting, which may be an oxygenated boron compound, salts of organic hydroxy acids.

In the next phase, US 4,551,176 (Slag et al.) described a composition of BS cements based on ground cement clinker without gypsum with a specific surface area of 150 to 3,000 m/kg and with a fraction of particles smaller than 5 microns in the range of 5 to 95% by weight, with 0.1 to 5% by weight of sulfonated polyphenolate (optionally containing quinone groups) and doped with salts of Al, Fe or Cr and with 0.1 to 10% of a compound from the group of alkali hydroxides, carbonates, bicarbonates, silicates and finally at least 20% of mixing water.

Technological aspects of these BS cements have been described in other publications.

A method of grinding cement clinker from AO 175 802 in the presence of lignin sulfonate in powder form as a grinding intensifier in a concentration of 0.2 to 4% by weight of clinker is known.

AO 195 787 discloses a method of grinding hydraulically active materials with the addition of one or more lignin-based substances in a concentration of 0.01 to 10% by weight, where the basic building block of these substances are p-oxy-m-raethoxyphenol cores with a propane or propylene chain terminated by an alcoholic or aldehyde group. These substances as grinding intensifiers have grains ranging from 0.01 micrometer to 15 mm. AO 227 205 describes a method of grinding hydraulically active substances, in particular cement clinker, in the presence of powdered lignin sulfonate, powdered alkali carbonate and possibly powdered sulfonated polyphenolate. The preparation of materials from BS cements with a higher specific surface area at a low water coefficient requires a different preparation method, which is accompanied by a higher energy consumption during wetting (grinding) of the binder, as follows from AO 202 771.

The disadvantages of the current solution for the preparation and use of BS cements are outlined below. When using powdered lignin sulfonate as a grinding additive, an energy-intensive raw material is used, which means significant energy consumption when drying sulfite liquors. During the actual grinding, technological difficulties arise due to the necessary precise dosing of the powdered grinding additive into the mill, when the vast majority of known and used technical solutions for grinding cements to a higher specific surface are based on precise dosing of liquid grinding additives.

When preparing BS cements with two additives (solution AO 202 771), further technological difficulties arise when grinding to a higher specific surface area with two minor additives (e.g. lignin sulfonate and Na^CO^), where there are particular difficulties in maintaining the exact content of both substances in the cement.

From a chemical point of view, it is necessary to mention another aspect, namely that in the presence of both additives (e.g. lignin sulfonate and Na^CO^) during their dissolution in water (in the mixture), a simultaneous reaction of clinker with water occurs, at an unequal rate. Compared to BS cements, which are processed with additives previously dissolved in water, these mixtures have a shorter initial setting time and a higher viscosity, i.e. worse workability. Technological problems also arise due to the wetting of soda during storage.

The presence of both additives in powder form also means that more intensive processing (grinding) of mixtures made from BS cements is necessary, as follows from AO 202 771.

Experimental work has led to the results that are the subject of the invention, which eliminates the above disadvantages. The essence of the invention is a binder based on hydraulically active substances, in particular cement clinker, containing 75.54 to 51.9% by weight of ground cement clinker with a specific surface area of 250 to 800 m^/kg, optionally with 0.01 to 0.2% of known grinding additives such as e.g. ethylene glycol, triethanolamine, further 0.2 to 4% of an alkaline salt or hydroxide, e.g. Na^CO^, K^CO^, NaHCOg, Na^SiO^; 0.2 to 3% of a sulfonated polyelectrolyte such as e.g.

lignin sulfonate, chemically modified lignin sulfonate, sulfonated lignin, sulfonated polyphenolate up to 3% of known setting regulators for gypsum-free cements such as phosphates, silicic acid derivatives, monosaccharides and their oxidation and reduction products, boric acid, salts of organic hydroxy acids, acrylic acid derivatives and possibly other known additives for gypsum-free cements such as substances with antifoaming effects in a concentration of

0.001 to 0.1% by weight and/or 0.05 to 20% SiC^ with a specific surface area of 5,000 to 200,000 m/kg, which contains more than 50% of particles smaller than 5 microns, optionally at least 20% water and further containing 0.005 to 0.5% of alkylolamides of linear alkylarylsulfonic acids or alkylolamides of sulfated fatty acids, optionally their salt mixtures of these alkylolamides with esteramines or esteramides of these acids, where the number of carbon atoms in the alkyl acid is 10 to 20 and all weight percentages are based on the weight of the clinker.

The alkanolamine derivatives mentioned may be, for example, ethanolamides of sodium dodecylbenzenesulfonate, optionally in a mixture with etheramines or esteramides, sulfated oleic acid monoethanolamide, sulfated coconut acid monoethanolamide, etc.

Alkalolamine derivatives in combination with a sulfonated polyelectrolyte (e.g. a lignin derivative), a sulfonated polyphenolate and an alkaline compound such as carbonate, bicarbonate delay the onset of solidification of mixtures and improve their workability (fluidity). Alkalolamine derivatives can be added directly to the grinding or to the mixing water.

These substances act as clinker grinding intensifiers even at low concentrations, at which, for example, powdered lignin sulfonate according to AO 175 802 and 195 787 is practically ineffective.

The use of these substances then enables easier preparation of mixtures with a low water coefficient, because there is better (faster) wetting of the particle surface. The simultaneous presence of alkanolamine and sulfate or sulfone groups in the substance molecule favorably affects the hydration process and allows achieving higher strengths (especially initial ones) than with known compositions.

BS cements, especially in comparison with the method where powdered lignin sulfonate was used as a grinding additive. When using these substances, the difficulties in preparing BS cements at a low water coefficient (forced longer grinding) are largely eliminated, as was shown in AO 202 771.

Another new phenomenon is the ability of alkanolamine derivatives to stabilize the onset of setting of BS cements under various disruptive conditions. The presence of alkanolamine derivatives delays the onset of setting (in a mixture with sulfonated polyelectrolyte and carbonate) more significantly than when using the polyelectrolyte and carbonate alone or when using known grinding additives, e.g. powdered lignin sulfonate according to AO 175 802 and 195 787, or according to US 3 689 294 (e.g. when using alkylated sodium diphenyloxide disulfonate).

«

The influence of the aforementioned alkanolamine derivatives on the properties of gypsum-free cements is unknown and cannot be deduced from the current state of the art.

The invention is illustrated in the following examples without limiting it.

All weight percentages are based on the weight of cement (ground clinker). Strengths given after 2 or 4 hours are always after 2 or 4 hours from the setting of the mixture, not from the preparation of the mixture. In some cases, the examples also use values according to the empirical visual scale of slurry workability (in addition to viscosity values) to evaluate rheological properties. These values were determined by visual assessment according to the following scale:

Workability

... preaches unworkable, dry

... the slurry only flows at 50 Hz vibration

... the porridge only flows when you tap the mixing bowl

... the slurry flows out of the mixing bowl by gravity

... the porridge is freely liquid

... the slurry is freely flowing with low viscosity ₄ When preparing the test specimens, the prepared specimens were always placed in the middle after preparation!

saturated water vapor for 24 hours and then in water at a temperature of 20 °C for up to 28 days.

Example 1

Clinker from the Lochkov cement plant was pre-crushed in a jaw crusher and a fraction with particles smaller than 2.5 mm was prepared for further grinding. The pre-crushed clinker was then ground for the same time in the presence of 3 different grinding additives. When using 0.1% ethylene glycol as a grinding additive, a specific surface area of 600 m/kg was achieved, when using 0.05% triethanolamine, a specific surface area of 610 m/kg was achieved.

When using sodium triethanolamidedodecylbenzenesulfonate at a concentration of 0.04%, a specific surface area of 630 m2/kg was achieved.

Example 2

Clinker from the Lochkov cement plant ground in the presence of 0.1% ethylene glycol (hereinafter referred to as ETG) - process according to US 3,689,291 - and according to the invention in the presence of 0.04% sodium triethanolamidedodecylbenzenesulfonate (hereinafter referred to as TEDB). Slurries were prepared from both cements with the addition of 1% Na ₂ CO ₂ and 0.4% sulfonated sodium ferric polyphenolate. The properties of the slurries are given in the following table:

Table

Specific surface area of cement (m^/kg) Grinding additive w Initial setting (min) viscosity (Pass) 600 ETG 0.25 50 1.45 600 ETG 0.24 40 1,603 600 ETG 0.22 30 more than 3.5 600 ETG 0.21 unprocessable porridge 630 TEDB 0.25 70 1.20 630 TEDB 0.24 60 1.49 630 TEDB 0.22 55 2.00 630 TEDB 0.20 40 2.67 w - water coefficient (water/cement)

Example 3

Cement was ground from clinker from the Lochkov cement plant with the addition of 0.03% sodium triethanolamidedodecyl2-benzenesulfonate (TEDB) to a specific surface area of 600 m/kg. Slurries were prepared from this cement with the addition of 0.4% sulfonated sodium ferric polyphenolate.

In some cases, TEDB was added at a concentration of 0.05% to the mixing water. The presence of TEDB in the mixing water prolonged the onset of setting, as shown in the following table:

Table

Start of setting (min) w TEDB as grinding additive TEDB as grinding additive + TEDB in mixing water

0.25 70 180 0.24 60 160 0.21 45 100 0.20 40 60 Example

Cement prepared by grinding in a circulating mill according to the procedures of AO 175 ₁ 802195 ₁ 787 and 227 ₍ 205 (grinding of clinker with 1% powdered sodium lignin sulfonate and 0.8% powdered Na ₂ CO^) from clinker from the Hranice cement plant was used for the preparation of cement slurry. This product had a specific surface area of 690 m^/kg. In a ball mill with a capacity of 50 l, cement 2 was prepared from the same clinker by grinding clinker with additives of 0.03% TEDB to a specific surface area of 660 m/kg. The same additives were used for the preparation of cement in a pilot mill (i.e. 1% sodium lignin sulfonate + 0.8% Na^CO^) with the difference that they were dissolved in the mixing water. When preparing slurry from cement from the circulating mill, it was necessary for the preparation of a liquid slurry at w = 0.26, stir (spread) the mixture for about 1 to 1.5 minutes. When preparing a slurry from the product according to the invention, a mixing time of less than 30 seconds was sufficient to prepare a freely flowing slurry at w = 0.23. This difference in the liquefaction rate of the two compared mixtures is striking due to the use of different grinding additives.

Example 5

For the preparation of quartz sand mortars, cement with a specific surface area of 600 m/kg was used, prepared by grinding clinker from the Lochkov cement plant in the presence of 0.03% TEDB as a grinding additive. 1% Na ₂ CO ₃ and 0.7% sulfonated sodium polyphenolate were dissolved in the mixing water.

0.05% TEDB was added as an additional additive. The cement to sand ratio in the mortar was 1:3 by weight, with the sand consisting of 3 fractions in a weight ratio of 1:1:1. The mortar was well workable at w = 0.29 and had the onset of setting after 50 minutes. When using the same sand (1.3 by weight) with an optimized fraction ratio, the mortar was practically fluid at w = 0.29 and had the onset of setting after 4.5 hours.

Example 6

A slurry (w = 0.25) prepared from cement with a specific surface area of 630 m/kg (ground in the presence of _{0.04% TEDB) and additives of 1% Na2CO3 and} 0.4% sufonated sodium ferric polyphenolate and 0.05% -sTEDB (in Thames water) was mixed after preparation with a laboratory high-speed mixer for

J, 2, 5 and 10 minutes respectively. The slurries had practically the same onset of solidification in the range of 170 to 180 minutes fexample 7

A product with a grain size smaller than 2 mm was sorted from the pre-crushed clinker from the Lochkov cement plant. This product was ground in a 50 l ball mill with various grinding additives, always with the same grinding charge and for the same time. Powdered sodium lignin sulfonate (LS), TEDB and a mixture of sulfated monoethanolamide of oleic acid and tetraglycol ether (ETA) were used as grinding additives. The obtained cement was used for the preparation of slurries with a low water coefficient and their properties are given in the following table:

Table

Grinding additive Specific surface area w Workability Compressive strength (m ² /kg) (PMa) hrs 24 hrs 7 days 28 days as additives in mixing water: Na^CO^ + 0.4% sulfonated sodium ferric polyphenolate

0.3% LS 520 0.23 3 4 63.5 77 102.5 0.05% TEDB 560 0.23 5 9.3 68.5 88.5 99 3.1% ETA 550 0.24 5 4.5 66.5 83.5 107.5 0.22 4 to 5 7.5 65 80 110 0.21 4 8.3 70.1 89 112 as ingredients in mixing waters: 1% _Na2CO3 + _0.8 % lignin sulfonate sodium ] free from monosaccharides 0.3% LS 520 0.23 4 4 56 - - 0.05% TEDB 560 0.23 5 7.5- - 66 - -

Note: A commercial defoamer was used in the preparation of the mash at a concentration of 0.02%.

__ When using lignisulfonate as a grinding additive, it was not possible to prepare a slurry at w = 0.20 to 0.22 with a processability better than 1 to 2 (according to the empirical processability scale).

Example 8

Clinker from the Hranice cement plant was ground with the addition of 0.1% ethylene glycol (procedure according to 2

US 3j689,294) cement with a specific surface area of 510 m /kg. A slurry with w = - 0.23 and workability according to the empirical scale of 4 to 5 was prepared from this cement, when the additive was used

1% Na ₂ C0 ₃ and 0.04% sulfonated sodium polyphenolate·· ferrous. in the second case was the same ingredients and into the water was added according to the invention 0 .03% of the ingredients ETA (see example 7) the qualities of porridge are listed in the following table: Table %ETA Start of solidification (min) Fortresses in 2 hours pressure (PMa) 24 hours 0 35 5.3 60.5 0.03 120 5.5 58

Note: 0.02% commercial defoamer was used in the preparation of the slurry.

Example 9

Cement was prepared from clinker from the Lochkov cement plant by grinding with 0.2% of the grinding additive, which was sodium tetrapropylene diphenoxide disulfonate (DF) - process according to US 3,689,294 - to a specific surface area

680 m/kg. Cement was prepared from the same clinker according to the invention by grinding with 0.04% TEDB as 2 grinding additives to a specific surface area of 630 m/kg. The properties of the prepared slurries are in the following table:

Table

Grinding additives in mixing water w Start of solidification (min) processed- Compressive strength (MPa) ability 2 hours 4 hours 24 hours 28 days DF 1% soda + 0.4% 0.21 30 3 7 12 68 96 Kortan FM TEDB 1% soda +0.4% 0.21 45 4 16 34 81 109 Kortan FM TEDB 1.3% soda + 0.9% oxidized lignin sulfonate 0.22 45 4 to 5 5 7 61 103 TEDB 1% soda + 0.5% 0.23 2 4 10 36 62 93

Sodium lignin sulfonate free of monosaccharides

Note: 0.02% of commercial defoamer was added to the sample water. Kortan FM - commercial product - sulfonated sodium ferric polyphenolate.

Example 10

Cement was prepared from clinker from the Lochkov cement plant by grinding to a specific surface area of 600 m/kg with the addition of 0.03% TEDB. From this cement, slurries with a low water coefficient were prepared, the properties of which are given in the following table:

Table

Ingredients w Processability Start of solidification (min) 1.5% soda + 0.9% oxidized lignin sulfonate 0.25 5 110 1.25% NaHCO ₃ + 0.6% Kofran FM 0.25 4 125 1% Na ₂ SiO ₃ + 4% oxidized ignin sulfonate 0.25 5 200 2.5% dose + 1% 0.25 5 90

lignin - 0.25 monosaccharide-free sulfonate + 0.4% sodium potassium tartrate

Other slurries were prepared from the same clinker, where ground cement (gypsum-free) was mixed with 1% finely ground gypsum. The slurry prepared at w « 0.25 with additives. 0.4% sulfonated sodium ferric polyphenolate and 1% Na^CO^^ had the onset of setting after 45 minutes and a viscosity of 2.13 Pas. After 10 to 15 minutes, the viscosity of the slurry increased so much that the freely flowing slurry had the character of a stiff paste. On the other hand, the slurry prepared with the same additives and at the same water coefficient, but in the absence of gypsum, had the onset of setting only after 65 minutes and during this time (practically within 60 minutes) a constant viscosity value of 1.29 Pas.

Another experiment with this cement was carried out by dry mixing this cement with 0.2% fine amorphous SiO ₂ (product KOMSIL). The slurry at w = 0.25 and the same additives as in the previous paragraph (without gypsum) had even lower viscosity values, namely 0.98 Pas.

Example 11

From clinker from the Čížkovice cement plant, which was ground to a specific surface area of 590 m/kg with the addition of 0.1% ethylene glycol, slurries with a low water coefficient were prepared. The properties of the slurries are given in the following table:

Table

Ingredients w Initial setting (min) Processability 1% soda + 0.4% 0.23 17 3 Kofran FM 1% soda + 0.4% Kortan FM + 0.05% Redb (in mixing water) 0.23 40 4 1.3% soda + 0.9% oxidized lignin sulfonate 0.24 55 4 1.3% soda + 0.9% oxidized lignin sulfonate + 0.05% TEDB (in mixing water) 0.24 100 5 From the same clinker was to grind cement for additives 0.06% TEDB 2 per specific surface 560 m /kg

The slurry processed at w = 0.24 with the addition of 1% soda and 0.4% Kortan FM began to set after 45 minutes.

Example 12

Clinker from the Prachovice cement plant was ground with the addition of 0.1% TEDB cement to a specific surface area of 340 m/kg. The slurry prepared at w = 0/25 with the addition of 0.9% sodium lignin sulfonate (free of monosaccharides) and 1.3% soda had a workability according to the empirical scale of 3 and the beginning of setting after 45 minutes. After the addition of 5 to 8% _SiO2 ^{fly ash} , ^{the workability improved} to level 4 to 5 and the beginning of setting was after 40 minutes.

Example 13

Cement with a specific surface area of 690 m2/kg was prepared from clinker from the Hranice cement plant in a circulating mill. The following grinding additives were used during grinding: 0.8% by weight of clinker powdered Na^CO^ and 1% by weight of clinker powdered sodium ligninsulfonate. This powdered sodium ligninsulfonate was produced by drying waste sulfite leaching, which was decalcified and partially freed from accompanying monosaccharides.

A slurry w « 0.26 with a consistency of 3 (empirical scale) was prepared from this cement and had an onset of setting after 70 minutes. In another experiment, a slurry with the same water ratio was prepared from the same cement, but 0.5% of the clinker weight of the additive TEDB was added to the mixing water. The onset of setting was extended to 90 minutes and the workability improved to a level of 4 (empirical scale).

Example 14

Cement was prepared from clinker from the Lochkov cement plant by grinding to a specific surface area of 620 m/kg with additives of 0.03% TEDB. No gypsum was added during grinding. Mortar with w = 0.30 was prepared from this cement. The sand to cement ratio was 2.5:1. The 0 to 6.3 mm fraction from Suchdol construction sand was used as sand. 1% by weight of soda and 0.6% of sodium ferric polyphenolate, 0.15% TEDB and 0.02% of commercial defoamer were added to the mixing water. A well-workable mortar was prepared by the following procedure: mixing water with additives was poured into the sand and the mixture was mixed briefly, cement was then poured into the mixed mixture and mixing continued for 1 minute. The prepared test specimens were stored after demolding in an environment of saturated water vapor. The mortar reached the following compressive strengths: 3 MPa 2 hours after setting, 9.8 MPa after 4 hours and 50 MPa after 24 hours.

Claims (1)

Binder based on hydraulically active substances, in particular cement clinker ground to a specific surface area of 250 to 800 m / kg containing 0.01 to 0.2% of known grinding additives such as ethylene glycol, triethanolamine; 0.2 to 4% of an alkali salt or hydroxide, for example Na ₂ CO ₃ , I <2 ^CO 3, NaHCO 3, KHCO ₃ , Na ₂ SiO ₃ ; 0.2 to 3% of sulfonated polyelectrolyte such as lignin sulfonate, chemically treated lignin sulfonate, sulfonated lifine, sulfonated polyphenolate, and up to 3% of known solidification regulators of gypsum-free cements such as phosphate, silicic acid derivatives, monosaccharides and their oxidation and reduction products, boric acid, salts of organic hydroxy acids and other known additives for gypsum-free cements such as antifoams and / or 0.05 to 20% SiO, with a specific surface area of 5,000 to 2 200 000 m / kg containing more than 50% of particles smaller than 5 micrometers and, if appropriate, at least 20% of water, characterized in that it contains from 0.005 to 0.5% of alkylolamides of linear alkylarylsulphonic acids or of alkylolamides of sulphated fatty acids or their salts or alkylolamides with etheramides or ester amides of these acids, wherein the number of carbon atoms in the acid alkyl is 10 to 20 and all percentages by weight are based on the weight of the clinker.